CN100364889C - Method for synthesizing flokite - Google Patents
Method for synthesizing flokite Download PDFInfo
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- CN100364889C CN100364889C CNB2005100806339A CN200510080633A CN100364889C CN 100364889 C CN100364889 C CN 100364889C CN B2005100806339 A CNB2005100806339 A CN B2005100806339A CN 200510080633 A CN200510080633 A CN 200510080633A CN 100364889 C CN100364889 C CN 100364889C
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Abstract
This invention provides a method for synthesizing mordenite, which takes brei starch as the template agent to add it into an initial gel mixture prepared with alkali material, silicon and Al raw substances to become a reacted mixture gel then to be hydrothermal-crystallized to get the mordenite, in which, the mol ratio of the compositions of the gel mixture according to its oxide is: M2O : SiO2 : Al2O3 : H2O=2-100 : 9-550 : 1 : 100-9000, and M is alkali metal.
Description
Technical field
The present invention relates to chemical material field, be specifically related to a kind of synthetic method of mordenite.
Background technology
Mordenite is a kind of molecular sieve with octatomic ring and the mutual decussate texture of twelve-ring, and chemical ingredients mainly comprises silicon and aluminium.Because it has higher silica alumina ratio, heat and hydrothermal stability, present unique catalytic performance, so mordenite has been widely used in such as in the reactions such as hydrogenation, alkylation, isomerization, disproportionation, catalytic cracking, transalkylation, dewaxing pour point depression and methyl alcohol amination, simultaneously also be used as the sepn process that sorbent material is widely used in gas or liquid mixture, thereby be a kind of very important functional inorganic materials.
Mordenite, though natural mordenite zeolite and general method synthetic mordenite, its silica alumina ratio (SiO
2/ Al
2O
3Mol ratio) is generally 9-12, promptly conventional mordenite.The mordenite of silica alumina ratio more than 15 called high silicon mordenite, and the silica alumina ratio scope of high silicon mordenite is generally at 15-30.Can with reference to disclosed summary document (Zeolites, 1986,6 (1): 2-8) and (petrochemical complex, 1988,17:528-534).
First since the synthesizing flokite, numerous investigators once carried out a large amount of study on the synthesis work from Barrer in 1948.It is mutually unusual with the aluminium source to remove used silicon source, the selection of additive reagent or structure directing agent when main research is all that hydro-thermal is synthetic.At present organic directed agents of being adopted of synthesizing flokite is more, as tetraethyl-ammonium salt (USP4,366,135 and USP4,525,466); Tetrapropyl ammonium salt (USP4,707,345 and USP4,788,380); Trolamine, 2-amino-2-ethyl-1, ammediol, dioxane or morpholine (USP4,337,502); Hexamethylene imine, 1,4-phenodiazine suberane, heptamethylene imines, suberane amine, hexamethylene alkanamine or pentamethylene amine (Chinese patent application number 00116530); 3-(dimethyl) amino-2,2-dimethyl propyl alcohol (USP4,376,104); 2-aminopyridine (USP4,390,457); Organic dye (USP4,585,640) such as methyl violet rowland 2B, methylene blue, methyl violet rowland or methyl green; 1-aminomethyl-1-hexalin (USP5,173,282); 1,2-diamino-cyclohexane (USP5,211,935); 1, the 8-diamino is to alkane in the Meng (USP5,219,547) etc.But, the structure directing agent that above-mentioned quilt uses in a large number mostly is organic amine, and not only its cost of material is more expensive, and the building-up process complex process.
In general adopt higher synthesized gel rubber silica alumina ratio, help to obtain the mordenite product of high silica alumina ratio (framework si-al ratio on the mordenite), and the mordenite product of high silica alumina ratio is compared with the mordenite product of low silica-alumina ratio on use properties and is had many superiority, for example heat and hydrothermal stability raising.Therefore the method that how to obtain with the gel synthesizing flokite of high silica alumina ratio is desired.But in the method for present known synthesizing flokite, the silica alumina ratio of the synthesized gel rubber of use is generally 10-200.And according to existing method, the silica alumina ratio of artificial increase synthesized gel rubber can cause the reduction of failure of mordenite synthetic or degree of crystallinity.The reduction of degree of crystallinity is very disadvantageous to the use of mordenite.
In addition, the existing knowledge of association area is told us, adopt different methods synthetic zeolite product often to have different use propertieies, for example, with quaternary ammonium salt method template agent method synthetic ZSM-5 zeolite with 1,6-hexanediamine template agent method synthetic ZSM-5 zeolite shows different catalytic performances when some reactions of catalysis.The method of new synthesizing flokite occurs so people also wait in expectation, and expects the use properties that synthetic mordenite product therefrom obtains.
Summary of the invention
The object of the present invention is to provide a kind of method of synthesizing flokite, starch with gelatinization is template, realize gel silica alumina ratio in the preparation process than broad, and the synthetic mordenite can have the performance when more higher than the sial of broad, and raw material sources are extensive, cheap, technological operation is convenient, the preparation process non-environmental-pollution.
Method according to synthesizing flokite provided by the invention comprises:
Alkaloid substance, silicon source material and aluminium source material are mixed with initial gel mixture, and this gel each component is M by the mol ratio of its oxide compound
2O: SiO
2: Al
2O
3: H
2O=2-100: 9-550: 1: 100-9000, wherein M represents basic metal;
The starch of gelatinization added in this initial gel mixture becomes reaction mixture gel, and to make the dry starch in this mixture (disregarding the water yield) and the mass ratio of initial gel mixture be 0.01-0.4;
Reaction mixture is warming up to 120-220 ℃, hydrothermal crystallizing 20-200 hour.
The starch of gelatinization of the present invention is meant the gelatinization product from ative starch or its treated starch, and the gelatinization point of described ative starch or its treated starch is 60-200 ℃.Preferably, described ative starch is the ative starch from fruit, treated starch is for by one or more the mixture of described ative starch in the various treated starches that modification obtained, for example, oxidation modification starch, acid degradation treated starch, cationic starch, alkaline degradation treated starch, esterification starch, etherification starch, graft starch, cross-linking starch, dextrin etc.The gelatinization point of preferred starch of the present invention and treated starch is 60-200 ℃, be preferably 80-100 ℃, and be warming up to its gelatinization point gelatinization certain hour after water mixes, can obtain pasted starch, this gelatinization process can carry out in normal pressure or pressure vessel, adds or do not add alkali lye.The gelatinization time of starch generally can be 5 minutes-36 hours, was preferably 3-24 hour.
About the gelatinization operation of starch can be with reference to " modified starch manufacturing and application " (Chemical Industry Press, 2001) of Zhang Yanping chief editor.
The preferable methods according to the present invention, ative starch adopts corn ative starch or potato ative starch, can directly adopt the commercial goods.
In the synthetic method provided by the present invention, the mass ratio of control dry starch and gel is 0.01-0.4, and preferred condition is 0.05-0.3.Starch pasting and preparation use during initial gel mixture alkaloid substance can be one or more mixture of sodium hydroxide, potassium hydroxide, lithium hydroxide.
Said aluminium source material is for comprising aluminium salt such as Tai-Ace S 150, aluminum nitrate, Wickenol CPS 325, comprising aluminate, aluminum oxide, aluminium hydroxides such as sodium aluminate, sodium metaaluminate, potassium metaaluminate in the inventive method, and the aluminium zeolite that contains of nature such as y-type zeolite, X type zeolite, A type zeolite or synthetic (containing the synthetic of aluminium zeolite can be referring to " structure of zeolite molecular sieve be with synthetic " of works such as Xu Ruren, Pang Wenqin, Tu Kungang, the mixture of one or more Changchun: press of Jilin University, 1987).
Said silicon source material is one or more the mixture in water glass, silicon sol, silicon gel or the silica gel in the inventive method.Wherein preferred silicon source is a silicon sol.
When the preparation initial gel mixture, look used silicon source material and aluminium source physical property, also can not add above-mentioned alkaloid substance, for example aluminate, aluminium hydroxide, water glass etc. in addition.And can realize step by step also in the preparation process that for example, the preliminary directed agents of preparation further is prepared into needed initial gel mixture more earlier.
The method according to this invention can and be used for by one or more modes in stirring, line-blending, the centrifugal mixing realizing to the mixing of each component, and the blended temperature can be from room temperature to 100 ℃, preferably mixes being no more than under 40 ℃ the temperature.
To resulting reaction mixture gel, through checking its pH to be preferably in 9-13.8, can implement hydrothermal crystallizing, can use withstand voltage reactor, the condition of hydrothermal crystallizing is under 120-200 ℃ and autogenous pressure crystallization 20-200 hour, and preferred condition is 140-180 ℃ of following crystallization 36-96 hour.
PH as mixture is too high or too low, then needs to add earlier acid solution or alkali lye and adjusts, and except that using above-mentioned alkali, the acid solution of selecting for use can be one or more the mixture in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, ammonium chloride, ammonium sulfate, the ammonium nitrate etc.
Hydrothermal crystallizing of the present invention can be known any method, for example one or more modes and the usefulness of stationary crystallization, step dynamic crystallization process, wherein preferably static crystallization and step dynamic crystallization process.
Product after crystallization is finished after filtration, washing, drying, can remove starch by roasting in case of necessity, promptly makes molecular screen primary powder of the present invention.
The synthetic method of mordenite provided by the present invention principal character compared with prior art is that this method is to make template with the starch of gelatinization to get by hydrothermal crystallizing.Gel silica alumina ratio wide ranges in synthetic can reach 9-550; The finished product silica alumina ratio scope can reach 10-15.Further measurement result shows, is the phase time degree of crystallinity ratio relative crystallinity high 10-30% of conventional tetraethyl ammonium hydroxide (TEAOH) for the mordenite of template preparation of the mordenite of template preparation according to method starch of the present invention.
Therefore, method provided by the invention institute synthetic mordenite, remove and to be widely used in the general application scenario of mordenite (such as catalysts such as hydrogenation, alkylation, isomerization, disproportionation, catalytic cracking, transalkylation, dewaxing pour point depression and methyl alcohol aminations, also be used as sorbent material) outside, compare with general method (as being the synthetic method of template with tetraethyl ammonium hydroxide) synthetic mordenite, be particularly suitable for catalytic conversion of heavy oil, can obviously improve the transformation efficiency of heavy oil, improve lightweight oil (as gasoline and diesel oil) yield.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) figure of the mordenite sample that synthesized according to embodiment 1.
Fig. 2 is X-ray diffraction (XRD) figure of the mordenite sample that synthesized according to embodiment 2.
Fig. 3 is X-ray diffraction (XRD) figure of the mordenite sample that synthesized according to Comparative Examples 1.
Embodiment
Below by embodiment will the present invention is further illustrated, purpose is to help the reader to understand essence of the present invention, but does not limit practical range of the present invention with this.
Illustrate: in each embodiment, relative crystallinity is with product and the standard specimen ratio value representation of the peak height sum of four the XRD diffraction peaks (25.63 °, 26.25 °, 27.68 °, 27.87 °) of 2 θ angles between 25-30 ° of X-ray diffraction (XRD) separately, because synthesis condition is different, the XRD diffraction peak of products obtained therefrom may be slightly different.Standard specimen herein (stipulating that its degree of crystallinity is 100%) is the resulting sample of tetraethyl ammonium hydroxide (TEAOH) method (Comparative Examples 1) with routine.
Embodiment 1
(1) takes by weighing 40g corn ative starch (commercial goods), add distilled water 400g, be stirred to its dissolving, put 100 ℃ of gelatinization 18h then and promptly get pasted starch.
(2) 122g water and 16g sodium hydroxide (purity 96%) are mixed stirring and dissolving; Add SiO then successively
2Content is 28% silicon sol (commercial goods) 93g, 7.6g NaY (commercial goods or synthetic with reference to open source literature), stirring 20min respectively makes it to mix, initial gel mixture, wherein the ratio between each raw material (press the oxide molecule mol ratio, below identical) is:
SiO
2/Al
2O
3＝53，
Na
2O/SiO
2＝0.43，
H
2O/SiO
2＝24；
(3) starch after the gelatinization (1) is added in the gel (2), stir 20min, it is transferred to withstand voltage reactor in 160 ℃ of crystallization 72 hours.Crystallization makes withstand voltage reactor naturally cool to room temperature after finishing.Mixed solution after the crystallization is filtered, wash drying with water, promptly get the mordenite product.2 gram products are put into retort furnace, be warming up to 540 ℃ of constant temperature calcinings 10 hours removing starch, thereby obtained the sample after the roasting.Show that through XRD analysis product is the crystal phase structure (as shown in Figure 1) of mordenite.
The relative crystallinity of sintetics is 115%, and fluorometry is measured its SiO
2/ Al
2O
3Be 10.
(1) takes by weighing 40g quaternary ammonium cation starch (commercial goods, substitution value=0.02), add distilled water 400g and sodium hydroxide (purity 96%) 0.8g, be stirred to its dissolving, put 100 ℃ of oil bath gelatinization 3h then and promptly get pasted starch.
(2) take by weighing water 122g, sodium hydroxide (purity 96%) 16g, stirring and dissolving; Add SiO then successively
2Content is 28% silicon sol (commercial goods) 93g, dried conventional NaY (commercial goods or synthetic with reference to open source literature) 7.6g, stirring 20min respectively makes it to mix, get initial gel mixture, wherein the ratio between each raw material (by the oxide molecule ratio) is:
SiO
2/Al
2O
3＝53，
Na
2O/SiO
2＝0.43，
H
2O/SiO
2＝24；
(3) pasted starch (1) is added in the gel (2), stir 20min, it is transferred to withstand voltage reactor in 160 ℃ of crystallization 3 days.Crystallization is taken out withstand voltage reactor after finishing from baking oven, make it to naturally cool to room temperature.With the product distilled water wash, suction filtration to product pH value is below 9, and filter cake is put into 100 ℃ of dried overnight of baking oven, promptly obtains the exsiccant product.A certain amount of product is put into retort furnace, and temperature programming to 540 ℃ constant temperature calcining 10h to be removing starch, thereby obtained the sample after the roasting.Show that through XRD analysis product is the crystal phase structure (as shown in Figure 2) of mordenite.
The relative crystallinity of sintetics is 125%, and fluorometry is measured its SiO
2/ Al
2O
3Be 12.
Embodiment 3
(1) takes by weighing 40g quaternary ammonium cation starch (commercial goods, substitution value=0.02), add distilled water 400g, be stirred to its dissolving, put 100 ℃ of following gelatinization 18h then and promptly get pasted starch.
(2) 271.5g water and 27.5g sodium hydroxide (purity 96%) are mixed stirring and dissolving; Add SiO then successively
2The silicon sol of content 28% (commercial goods) 214.3g, 1.56g Al (OH)
3, stir 20min respectively and make it to mix, get initial gel mixture, wherein the ratio between each raw material (by the oxide molecule ratio) is:
SiO
2/Al
2O
3＝100，
Na
2O/SiO
2＝0.33，
H
2O/SiO
2＝24；
(3) starch after the gelatinization (1) is added in the gel (2), stir 20min, add sulfuric acid adjust pH to 12.0, it is transferred to withstand voltage reactor stirred crystallization 48 hours in 180 ℃.Crystallization makes withstand voltage reactor naturally cool to room temperature after finishing.Mixed solution after the crystallization is filtered, wash drying with water, promptly get the mordenite product.2 gram products are put into retort furnace, be warming up to 540 ℃ of constant temperature calcinings 4 hours removing starch, thereby obtained the sample after the roasting.Show that through XRD analysis product is the crystal phase structure of mordenite.The X-ray diffraction of sample (XRD) figure is similar with example 2, therefore no longer lists.
The relative crystallinity of sintetics is 120%, and fluorometry is measured its SiO
2/ Al
2O
3Be 12.
Embodiment 4
(1) takes by weighing 20g quaternary ammonium cation starch (commercial goods, substitution value=0.02), add distilled water 200g, be stirred to its dissolving, put 100 ℃ of following gelatinization 14h then and promptly get pasted starch.
(2) 380g water and 25g sodium hydroxide (purity 96%) are mixed stirring and dissolving; Add SiO then successively
2The silicon sol of content 28% (commercial goods) 214.3g, 3.33gAl
2(SO
4)
318H
2O (commercial reagent, purity 99%) stirs 20min respectively and makes it to mix, and gets initial gel mixture, and wherein the ratio between each raw material (by the oxide molecule ratio) is:
SiO
2/Al
2O
3＝200，
Na
2O/SiO
2＝0.30，
H
2O/SiO
2＝30；
(3) starch after the gelatinization (1) is added in the gel (2), stir 20min, add nitric acid adjust pH to 13.0, it is transferred to withstand voltage reactor in 170 ℃ of crystallization 68 hours.Crystallization makes withstand voltage reactor naturally cool to room temperature after finishing.Mixed solution after the crystallization is filtered, wash drying with water, promptly get the mordenite product.2 gram products are put into retort furnace, be warming up to 540 ℃ of constant temperature calcinings 4 hours removing starch, thereby obtained the sample after the roasting.Show that through XRD analysis product is the crystal phase structure of mordenite, the X-ray diffraction of sample (XRD) figure is similar with example 2, therefore no longer lists.
The relative crystallinity of sintetics is 115%, and fluorometry is measured its SiO
2/ Al
2O
3Be 12.
Embodiment 5
(1) takes by weighing 20g quaternary ammonium cation starch (commercial goods, substitution value=0.02), add distilled water 200g, be stirred to its dissolving, put 100 ℃ of gelatinization 10h then and promptly get pasted starch.
(2) 386g water and 24.5g sodium hydroxide (purity 96%) are mixed stirring and dissolving; Add SiO then successively
2The silicon sol of content 28% (commercial goods) 214.3g, 1.13g NaAlO
2(contain Al
2O
345%), stirring 20min makes it to mix and obtains gel, and wherein the ratio between each raw material (by the oxide molecule ratio) is:
SiO
2/Al
2O
3＝200，
Na
2O/SiO
2＝0.30，
H
2O/SiO
2＝30；
(3) starch after the gelatinization (1) is added in the gel (2), stir 20min, add hydrochloric acid adjust pH to 12.0, it is transferred to withstand voltage reactor in 170 ℃ of crystallization 70 hours.Crystallization makes withstand voltage reactor naturally cool to room temperature after finishing.Mixed solution after the crystallization is filtered, wash drying with water, promptly get the mordenite product.2 gram products are put into retort furnace, be warming up to 540 ℃ of constant temperature calcinings 4 hours removing starch, thereby obtained the sample after the roasting.Show that through XRD analysis product is the crystal phase structure of mordenite.The X-ray diffraction of sample (XRD) figure is similar with example 2, therefore no longer lists.
The relative crystallinity of sintetics is 119%, and fluorometry is measured its SiO
2/ Al
2O
3Be 12.
Embodiment 6
(1) takes by weighing 20g quaternary ammonium cation starch (commercial goods, substitution value=0.02), add distilled water 200g, be stirred to its dissolving, put 100 ℃ of gelatinization 8h then and promptly get pasted starch.
(2) 359g water and 29.7g sodium hydroxide (purity 96%) are mixed stirring and dissolving; Add SiO then successively
2The silicon sol of content 28% (commercial goods) 381.25g, 3.8gNaX (synthetic with reference to open source literature), stirring 20min make it to mix and obtain gel, and wherein the ratio between each raw material (by the oxide molecule ratio) is:
SiO
2/Al
2O
3＝400，
Na
2O/SiO
2＝0.20，
H
2O/SiO
2＝20；
(3) starch after the gelatinization (1) is added in the gel (2), stir 20min, add hydrochloric acid adjust pH to 11.8, it is transferred to withstand voltage reactor in 180 ℃ of crystallization 60 hours.Crystallization makes withstand voltage reactor naturally cool to room temperature after finishing.Mixed solution after the crystallization is filtered, wash drying with water, promptly get the mordenite product.2 gram products are put into retort furnace, be warming up to 540 ℃ of constant temperature calcinings 4 hours removing starch, thereby obtained the sample after the roasting.Show that through XRD analysis product is the crystal phase structure of mordenite.The X-ray diffraction of sample (XRD) figure is similar with example 2, therefore no longer lists.
The relative crystallinity of sintetics is 122%.Fluorometry is measured its SiO
2/ Al
2O
3Be 14.
Embodiment 7
(1) takes by weighing 20g quaternary ammonium cation starch (commercial goods, substitution value=0.02), add distilled water 200g, be stirred to its dissolving, put 100 ℃ of gelatinization 8h then and promptly get pasted starch.
(2) 359g water and 48.6g potassium hydroxide (purity 82%) are mixed stirring and dissolving; Add SiO then successively
2The silicon sol of content 28% (commercial goods) 381.25g, 3.8g NaY (commercial goods or synthetic with reference to open source literature), stirring 20min make it to mix and obtain gel, and wherein the ratio between each raw material (by the oxide molecule ratio) is:
SiO
2/Al
2O
3＝400，
K
2O/SiO
2＝0.20，
H
2O/SiO
2＝20；
(3) starch after the gelatinization (1) is added in the gel (2), stir 20min, add hydrochloric acid adjust pH to 12.0, it is transferred to withstand voltage reactor in 180 ℃ of crystallization 48 hours.Crystallization makes withstand voltage reactor naturally cool to room temperature after finishing.Mixed solution after the crystallization is filtered, wash drying with water, promptly get the mordenite product.2 gram products are put into retort furnace, be warming up to 540 ℃ of constant temperature calcinings 4 hours removing starch, thereby obtained the sample after the roasting.Show that through XRD analysis product is the crystal phase structure of mordenite.The X-ray diffraction of sample (XRD) figure is similar with example 2, therefore no longer lists.
The relative crystallinity of sintetics is 120%, and fluorometry is measured its SiO
2/ Al
2O
3Be 15.
(1) gets high alkali deflection aluminium acid sodium and (contain Al
2O
33.1wt%, Na
2O 20.7wt%, H
2O 76.2wt%) 70g adds service water glass and (contains SiO
220.9wt%, Na
2O 6.9wt%, H
2O 72.2wt%) 60g puts 40 ℃ of stirring in water bath 2h, and making oxide mol ratio is 14.1Na
2O: 9.8SiO
2: 1Al
2O
3: 252H
2The directed agents of O is standby.
(2) get 20g quaternary ammonium cation starch (commercial goods, substitution value=0.02), add water 200g, add NaOH 0.4g again, be stirred to its dissolving, put 100 ℃ of gelatinization 5h then and promptly get pasted starch.
(3) water intaking 20g adds industrial aluminum sulphate and (contains Al
2O
37.0wt%, H
2O 76.5wt%) 50g under agitation adds service water glass and (contains SiO
220.9wt%, Na
2O 6.9wt%, H
2O 72.2wt%) 90g stirs 30min; Add directed agents 80g, stir 20min, making oxide mol ratio is 6.0Na
2O: 9.3SiO
2: 1.0Al
2O
3: 213.9H
2The initial gel of O; Add pasted starch then, stir 20min; The gained mixture is transferred to withstand voltage reactor in 180 ℃ of crystallization 68 hours.Crystallization makes withstand voltage reactor naturally cool to room temperature after finishing.Mixed solution after the crystallization is filtered, wash drying with water, promptly get the mordenite product.2 gram products are put into retort furnace, be warming up to 600 ℃ of constant temperature calcinings 6 hours removing starch, thereby obtained the sample after the roasting.Show that through XRD analysis product is the crystal phase structure of mordenite.The X-ray diffraction of sample (XRD) figure is similar with example 2, therefore no longer lists.
The relative crystallinity of sintetics is 112%, and fluorometry is measured its SiO
2/ Al
2O
3Be 10.
Embodiment 9
(1) takes by weighing 44g hydrochloric acid modified potato starch (commercial goods), add distilled water 400g and sodium hydroxide (purity 96%) 0.8g, be stirred to its dissolving, put 100 ℃ of oil bath gelatinization 3h then and promptly get pasted starch.
(2) take by weighing water 122g, sodium hydroxide (purity 96%) 16g, stirring and dissolving; Add SiO then successively
2The silicon sol of content 28% (commercial goods) 93g, dried conventional NaY (commercial goods or with reference to open source literature synthetic) 7.6g stirs 20min respectively and makes it to mix and obtain gel, and wherein the ratio between each raw material (comparing by oxide molecule) is:
SiO
2/Al
2O
3＝53，
Na
2O/SiO
2＝0.43，
H
2O/SiO
2＝24；
(3) pasted starch (1) is added in the gel (2), stir 20min, it is transferred to withstand voltage reactor in 160 ℃ of crystallization 3 days.Crystallization is taken out withstand voltage reactor after finishing from baking oven, make it to naturally cool to room temperature.With the product distilled water wash, suction filtration to product pH value is below 9, and filter cake is put into 100 ℃ of dried overnight of baking oven, promptly obtains the exsiccant product.A certain amount of product is put into retort furnace, and temperature programming to 540 ℃ constant temperature calcining 4h to be removing starch, thereby obtained the sample after the roasting.Show that through XRD analysis product is the crystal phase structure of mordenite.
The relative crystallinity of sintetics is 115%, and fluorometry is measured its SiO
2/ Al
2O
3Be 10.
(1) takes by weighing 45g hypochlorite oxidation starch (commercial goods), add distilled water 400g and sodium hydroxide (purity 96%) 0.8g, be stirred to its dissolving, put 100 ℃ of oil bath gelatinization 3h then and promptly get pasted starch.
(2) take by weighing water 122g, sodium hydroxide (purity 96%) 16g, stirring and dissolving; Add SiO then successively
2The silicon sol of content 28% (commercial goods) 93g, dried conventional NaY (commercial goods or with reference to open source literature synthetic) 7.6g stirs 20min respectively and makes it to mix and obtain gel, and wherein the ratio between each raw material (comparing by oxide molecule) is:
SiO
2/Al
2O
3＝53，
Na
2O/SiO
2＝0.43，
H
2O/SiO
2＝24；
(3) pasted starch (1) is added in the gel (2), stir 20min, it is transferred to withstand voltage reactor in 160 ℃ of crystallization 3 days.Crystallization is taken out withstand voltage reactor after finishing from baking oven, make it to naturally cool to room temperature.With the product distilled water wash, suction filtration to product pH value is below 9, and filter cake is put into 100 ℃ of dried overnight of baking oven, promptly obtains the exsiccant product.A certain amount of product is put into retort furnace, and temperature programming to 540 ℃ constant temperature calcining 4h to be removing starch, thereby obtained the sample after the roasting.Show that through XRD analysis product is the crystal phase structure of mordenite.
The relative crystallinity of sintetics is 115%, and fluorometry is measured its SiO
2/ Al
2O
3Be 12.
Embodiment 11
(1) takes by weighing 42g starch-phosphate (commercial goods), add distilled water 400g and sodium hydroxide (purity 96%) 0.8g, be stirred to its dissolving, put 100 ℃ of oil bath gelatinization 4h then and promptly get pasted starch.
(2) take by weighing water 122g, sodium hydroxide (purity 96%) 16g, stirring and dissolving; Add SiO then successively
2The silicon sol of content 28% (commercial goods) 93g, dried conventional NaY (commercial goods or with reference to open source literature synthetic) 7.6g stirs 20min respectively and makes it to mix and obtain gel, and wherein the ratio between each raw material (comparing by oxide molecule) is:
SiO
2/Al
2O
3＝53，
Na
2O/SiO
2＝0.43，
H
2O/SiO
2＝24；
(3) pasted starch (1) is added in the gel (2), stir 20min, it is transferred to withstand voltage reactor in 160 ℃ of crystallization 3 days.Crystallization is taken out withstand voltage reactor after finishing from baking oven, make it to naturally cool to room temperature.With the product distilled water wash, suction filtration to product pH value is below 9, and filter cake is put into 100 ℃ of dried overnight of baking oven, promptly obtains the exsiccant product.A certain amount of product is put into retort furnace, and temperature programming to 540 ℃ constant temperature calcining 4h to be removing starch, thereby obtained the sample after the roasting.Show that through XRD analysis product is the crystal phase structure of mordenite.
The relative crystallinity of sintetics is 117%, and fluorometry is measured its SiO
2/ Al
2O
3Be 10.
Embodiment 12
(1) takes by weighing 40g hydroxyethylamyle (commercial goods), add distilled water 400g and sodium hydroxide (purity 96%) 0.8g, be stirred to its dissolving, put 100 ℃ of oil bath gelatinization 5h then and promptly get pasted starch.
(2) take by weighing water 122g, sodium hydroxide (purity 96%) 16g, stirring and dissolving; Add SiO then successively
2The silicon sol of content 28% (commercial goods) 93g, dried conventional NaY (commercial goods or with reference to open source literature synthetic) 7.6g stirs 20min respectively and makes it to mix and obtain gel, and wherein the ratio between each raw material (comparing by oxide molecule) is:
SiO
2/Al
2O
3＝53，
Na
2O/SiO
2＝0.43，
H
2O/SiO
2＝24；
(3) pasted starch (1) is added in the gel (2), stir 20min, it is transferred to withstand voltage reactor in 160 ℃ of crystallization 3 days.Crystallization is taken out withstand voltage reactor after finishing from baking oven, make it to naturally cool to room temperature.With the product distilled water wash, suction filtration to product pH value is below 9, and filter cake is put into 100 ℃ of dried overnight of baking oven, promptly obtains the exsiccant product.A certain amount of product is put into retort furnace, and temperature programming to 540 ℃ constant temperature calcining 4h to be removing starch, thereby obtained the sample after the roasting.Show that through XRD analysis product is the crystal phase structure of mordenite.
The relative crystallinity of sintetics is 118%, and fluorometry is measured its SiO
2/ Al
2O
3Be 10.
(1) takes by weighing 25g dextrin (commercial goods), add distilled water 400g and sodium hydroxide (purity 96%) 0.8g, be stirred to its dissolving, put 80 ℃ of oil bath gelatinization 3h then and promptly get pasted starch.
(2) take by weighing water 122g, sodium hydroxide (purity 96%) 16g, stirring and dissolving; Add SiO then successively
2The silicon sol of content 28% (commercial goods) 93g, dried conventional NaY (commercial goods or with reference to open source literature synthetic) 7.6g stirs 20min respectively and makes it to mix and obtain gel, and wherein the ratio between each raw material (comparing by oxide molecule) is:
SiO
2/Al
2O
3＝53，
Na
2O/SiO
2＝0.43，
H
2O/SiO
2＝24；
(3) gelatinization dextrin (1) is added in the gel (2), stir 20min, it is transferred to withstand voltage reactor in 160 ℃ of crystallization 3 days.Crystallization is taken out withstand voltage reactor after finishing from baking oven, make it to naturally cool to room temperature.With the product distilled water wash, suction filtration to product pH value is below 9, and filter cake is put into 100 ℃ of dried overnight of baking oven, promptly obtains the exsiccant product.A certain amount of product is put into retort furnace, and temperature programming to 540 ℃ constant temperature calcining 4h to be removing dextrin, thereby obtained the sample after the roasting.Show that through XRD analysis product is the crystal phase structure of mordenite.
The relative crystallinity of sintetics is 120%, and fluorometry is measured its SiO
2/ Al
2O
3Be 12.
Embodiment 14
Respectively the present invention is pressed molecular sieve with the mordenite (embodiment 2) of starch method preparation with the mordenite (conventional zeolite) of tetraethyl ammonium hydroxide preparation: (NH
4)
2SO
4: H
2O=1: 1: 10 (weight ratio) exchanges 1h in 8O ℃ of water-bath, control pH=4.0.Washing, filtration, dry 4h in 120 ℃ of baking ovens.Sample drying is after 540 ℃ of roasting 4h.Molecular sieve after this once exchanges exchanges by above-mentioned condition and dry twice again.
With the 120 ℃ of dry 10h of molecular sieve after three friendships, one roasting, the dendrometry water yield; Press the molecular sieve butt then: kaolin: aluminium colloidal sol is (with Al
2O
3Meter)=and 35: 50: 15 mixed, add the less water making beating again; Be warming up to 540 ℃ of roasting 4h after drying; Sieve after grinding, get 40-60 order particle, obtain can be used as the mordenite of catalyzer through 750 ℃ of 100% water vapour hydrothermal aging 4h; The catalyzer of preparation is applied in the catalytic cracking reaction.
With grand celebration heavy oil (the 70wt% grand celebration subtracts four line wax oils+70% grand celebration vacuum residuum) is raw material, as catalyzer, estimates the cracking performance of mordenite catalyst with prepared mordenite with BPWF-1 type standard catalytic cracking micro-reactor.The micro anti-evaluation condition: temperature of reaction is 500 ℃, agent-oil ratio=3.2, WHSV (weight hourly space velocity)=19.The character of grand celebration heavy oil sees Table 1.Evaluation result sees Table 2.
As known from Table 2, with respect to the mordenite with the tetraethyl ammonium hydroxide preparation, the prepared mordenite of the present invention has high cracking activity, and its heavy oil conversion rate is high 15 percentage points, light oil (gasoline+diesel oil) yield is high 14 percentage points, and coke and liquefied gas yield slightly reduce.
Table 1 grand celebration heavy oil character
| Project | Subtract four line wax oils | Vacuum residuum |
| Density (20 ℃)/g.cm -3100 ℃ of viscosity/mm 2.s -1Carbon residue/wt% initial boiling point/℃ 500 ℃ distillates/wt% ultimate analysis/wt% C H N | 0.87 11.28 0.30 423 38 86.30 13.70 | 0.93 137.67 8.22 456 7 87.03 12.67 0.30 |
The crackate analysis of the mordenite of the conventional mordenite of table 2 and the present invention preparation during as catalyzer cracking grand celebration heavy oil
| Catalyzer | Conventional mordenite | The mordenite of the present invention's preparation | Changing value |
| Product yield/m% loss+dry gas liquefied gas C 5+ gasoline fraction diesel oil distillate heavy oil fraction coke light oil yield heavy oil conversion rate | 1.19 4.84 23.13 40.17 25.18 5.49 63.30 74.82 | 1.35 4.49 71.81 7.62 9.78 4.90 79.43 90.22 | 0.16 -0.35 48.68 -32.55 -15.40 -0.59 16.13 15.40 |
Comparative Examples 1
Under agitation add 224.6g distilled water, 12.5gNaOH (purity 96%), 66.6gAl successively
2(SO
4)
318H
2O (commercial reagent, purity 99%), SiO
2Content is that tetraethyl ammonium hydroxide (commercial goods) preparation of 30% silicon sol (commercial goods) 360g, 26.71g 10% consists of 1.5Na
2O: 18SiO
2: 1.0Al
2O
3: 0.75 (TEA)
2O: 375H
2The gel of O is adorned still in 180 ℃ of crystallization 48h with it.Crystallization is taken out withstand voltage reactor after finishing from baking oven, make it to naturally cool to room temperature.With the product distilled water wash, suction filtration to product pH value is below 9, and filter cake is put into 100 ℃ of dried overnight of baking oven, promptly obtains the exsiccant product.A certain amount of product is put into retort furnace, and temperature programming to 540 ℃ constant temperature calcining 4h to be removing tetraethyl ammonium hydroxide, thereby obtained the sample after the roasting.Show that through XRD analysis product is the crystal phase structure (as shown in Figure 3) of mordenite.
The relative crystallinity of sintetics is defined as 100%, and fluorometry is measured its SiO
2/ Al
2O
3Be 10.
Comparative Examples 2
Under agitation add 40g distilled water successively, (commercial goods contains Al to the 100g industrial aluminum sulphate
2O
37.0wt%, H
2O 76.5wt%), (commercial goods contains SiO to 545g service water glass
220.9wt%, Na
2O 6.9wt%, H
2O 72.2wt%), the tetraethyl ammonium hydroxide of 70g 10% (commercial goods) preparation consists of 9.1Na
2O: 27.7SiO
2: 1.0Al
2O
3: 0.37 (TEA)
2O: 464H
2The gel of O is adorned still in 180 ℃ of crystallization 48h with it.Crystallization naturally cools to room temperature with withstand voltage reactor after finishing.With the product distilled water wash, suction filtration to product pH value is below 9, and filter cake is put into 100 ℃ of dried overnight of baking oven, promptly obtains the exsiccant product.A certain amount of product is put into retort furnace, and temperature programming to 540 ℃ constant temperature calcining 4h to be removing tetraethyl ammonium hydroxide, thereby obtained the sample after the roasting.Show that through XRD analysis product is the crystal phase structure of mordenite.
The relative crystallinity of sintetics is defined as 102%, and fluorometry is measured its SiO
2/ Al
2O
3Be 10.
Claims (10)
1. the method for a synthesizing flokite comprises:
Alkaloid substance, silicon source material and aluminium source material are mixed with initial gel mixture, and each component is M by the mol ratio of its oxide compound in this gel
2O: SiO
2: Al
2O
3: H
2O=2-100: 9-550: 1: 100-9000, wherein M represents basic metal;
The starch of gelatinization added in this initial gel mixture becomes reaction mixture gel, and makes that the mass ratio of dry starch and initial gel mixture is 0.01-0.4 in this mixture;
This reaction mixture is warming up to 120-220 ℃, hydrothermal crystallizing 20-200 hour.
2. the described method of claim 1, wherein, the starch of described gelatinization is from the gelatinization product of ative starch or its treated starch, and the gelatinization point of described ative starch or its treated starch is 60-200 ℃.
3. the described method of claim 2, wherein, described treated starch comprises one or more the mixture by the oxidation modification starch of ative starch after modification, acid degradation treated starch, cationic starch, alkaline degradation treated starch, esterification starch, etherification starch, graft starch, cross-linking starch, dextrin.
4. claim 2 or 3 described methods, wherein, ative starch or its treated starch gelatinization time under gelatinization point is 5 minutes-36 hours.
5. the described method of claim 1, wherein, the used alkaloid substance of preparation initial gel mixture is one or more a mixture of sodium hydroxide, potassium hydroxide, lithium hydroxide.
6. the described method of claim 1, wherein, described aluminium source material is aluminium salt, aluminate, aluminum oxide, aluminium hydroxide or contains one or more mixture in the aluminium zeolite.
7. the described method of claim 1, wherein, described silicon source material comprises one or more the mixture in water glass, silicon sol, silicon gel or the silica gel.
8. the described method of claim 1, wherein, the mixing temperature of each component is a room temperature to 100 ℃ when preparation initial gel mixture and reaction mixture gel.
9. the described method of claim 1, wherein, described hydrothermal crystallizing operation comprises the combination of one or more modes in stationary crystallization, the step dynamic crystallization process.
10. the described method of claim 1, it also comprises: after crystallization is finished, after filtration, washing, drying, make molecular screen primary powder.
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| CN101549302B (en) * | 2008-04-03 | 2011-04-27 | 中国石油大学(北京) | Faujasite/Al2O3 composite material and preparation method thereof |
| CN102190316B (en) * | 2010-03-03 | 2013-01-09 | 中国石油化工股份有限公司 | Method for synthesizing mesoporous mordenite |
| JP5351216B2 (en) * | 2010-07-01 | 2013-11-27 | 日本化学工業株式会社 | Method for producing zeolite |
| CN102976354B (en) * | 2012-12-24 | 2014-03-19 | 厦门大学 | Method or synthesizing mordenite by using kaolin and quartz |
| CN104016371B (en) * | 2013-03-01 | 2016-03-16 | 上海碧科清洁能源技术有限公司 | The in-situ synthetic method of cupric mordenite |
| CN111086994B (en) * | 2018-10-23 | 2021-10-08 | 中国石油化工股份有限公司 | Method for synthesizing mesoporous high-crystallinity Y-type molecular sieve |
| CN114516640B (en) * | 2020-11-18 | 2024-04-16 | 中国科学院大连化学物理研究所 | Mordenite, preparation method and application thereof |
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|---|---|---|---|---|
| US4366135A (en) * | 1979-06-29 | 1982-12-28 | Montedison S.P.A. | Method for preparing zeolites |
| US5219547A (en) * | 1991-10-04 | 1993-06-15 | Mobil Oil Corp. | Synthesis of crystalline mordenite-type material |
| CN1201758A (en) * | 1997-06-06 | 1998-12-16 | 中国石油化工总公司 | Synthesis of mordenite with high silicon aluminum ratio |
| CN1328961A (en) * | 2000-06-15 | 2002-01-02 | 中国石油化工集团公司 | Synthesis method of high-silicon mordenite |
| CN1463921A (en) * | 2002-06-05 | 2003-12-31 | 中国科学院大连化学物理研究所 | Process for synthesizing high silicon content mordenite |
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|---|---|---|---|---|
| US4366135A (en) * | 1979-06-29 | 1982-12-28 | Montedison S.P.A. | Method for preparing zeolites |
| US5219547A (en) * | 1991-10-04 | 1993-06-15 | Mobil Oil Corp. | Synthesis of crystalline mordenite-type material |
| CN1201758A (en) * | 1997-06-06 | 1998-12-16 | 中国石油化工总公司 | Synthesis of mordenite with high silicon aluminum ratio |
| CN1328961A (en) * | 2000-06-15 | 2002-01-02 | 中国石油化工集团公司 | Synthesis method of high-silicon mordenite |
| CN1463921A (en) * | 2002-06-05 | 2003-12-31 | 中国科学院大连化学物理研究所 | Process for synthesizing high silicon content mordenite |
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